Textile finishing composition comprising an aqueous dispersion of the interaction product of urea, formaldehyde, a fatty acid amide and a primary amine



3,051,674 TEXTILE FINISHING COR/EOSITION CGMPRISWG AN AQUEOUS DISPERSIONOF TIE INTERAC- TION PRODUCT F UREA, FORMALDEHYDE, A FATTY ACID AIVHDEAND A PRIMARY AMINE Bernard H. Kress, Lafayette Hill, Pa., assignor toQuaker Chemical Products Corporation, Conshohocken, Pa., a corporationof Pennsylvania N0 Drawing. Filed May 25, 1959, Ser. No. 815,268 3Claims. (Cl. 26029.4)

This invention relates to novel compositions of matter which whenapplied to fibrous material impart certain durable effects. Such effectsas Water repellency and softness of hand may be imparted to suchmaterials which may be in the form of textiles, paper, felts, or Webs,etc., or as single fibers or yarns. Other effects on textiles may becrease resistance and shrinkage control contributing to wash-Wearproperties. These effects imparted by the compositions of this inventionare able to withstand the action of commercial and home launderingprocedures and dry cleaning processes.

The compositions of the invention are useful generally in application tocellulosic fibers and materials containing them such as woven andknitted fabrics, paper, and non-woven fabrics. Textiles containingcotton or regenerated cellulose fibers are specially benefited by theapplication of these compositions. Even mixtures containingnon-cellulosic fibers may be benefited by application of these newproducts: for example, cellulose acetate-cotton, and rayon-polyestermixtures have been treated beneficially.

Compositions of the present invention impart water repellency, asdistinct from Water proofness, to fibers treated therewith. Accordinglythe treated materials retain their air permeability, handle, and drape.The Water repellent characteristics as measured by spray rating areexcellent and are not greatly reduced by laundering or dry cleaning.

A number of additional valuable properties are imparted to fabrics bythese new compositions. The fiber properties are so modified by reactionwith these products that the crease resistance of the fabric isincreased. This is evident in the rise in crease angle (as measured bythe Monsanto crease resistance instrument) obtained on cotton fabrics.This efic'ect is resistant to laundering. This crease resistance isaccomplished without an unusual loss in tensile strength of the fabric.Another feature is that the damage to the fabric caused by Washing indilute, chlorine-bleaching solutions and thereafter ironing is very low.Under these conditions there is no color formation.

Application to regenerated cellulose products, e.g. cuprammonium orviscose rayon, imparts a dimensional control to the fabric together withWater repellency.

A desirable softening of fabrics is also accomplished by the applicationof the products of the invention; the effect is imparted in addition tothe crease proofing and dimensional control effects mentioned above.

Water repellent properties can be imparted to fabrics by various knowncompositions. For example, certain silicone liquids may be applied fromsolution or emulsion. It is well known that although these are veryeffective they are costly. Similarly various pyridine-containingcompositions, although they are less costly than the silicones have thedisadvantage of liberating pyridine during the processing of the fabric.This requires special equipment to take care of this bad-smellingby-product. These products because of their chemical nature do notimpart the added properties of crease resistance and dimensionalcontrol.

Certain heat reactive resins modified by steararnide have also been usedfor impartation of water repellency. They suffer from the disadvantageof imparting a harsh hand to the fabric and of not yielding wash-wearproperties.

The object of this invention is to provide novel compositions whichimpart Water repellency together with crease resistance and dimensionalcontrol to cellulosic fibers.

A further object is to provide novel compositions which are used readilyin textile treating equipment without the liberation of undesirableodors.

A still further object is to provide products which can be used togetherwith reactant finishes of the types disclosed in my copending U.S.applications Serial No. 665,- 138 filed June 12, 1957, now US. Patent2,917,411 and Serial No. 625,241 filed November 30, 1956, now U.S.Patent 2,895,923 to obtain special effects on cellulosic fibers andblends thereof with other fibers.

The compositions of my invention comprise the following ingredients: (a)a long chain fatty acid amide, (b) formaldehyde or a formaldehydeliberating compound such as paraformaldehyde, or methylal, (c) urea and(d) an amine taken from the group consisting of aliphatic mono anddiamines having 1 to 4 carbon atoms for each amino group and having onlyhydroxy and ether groups attached to the hydrocarbon chain attached toN.

The amides which I may use to prepare my compositions are simple amideshaving from 8 to 35 carbon atoms. Such substances as stearamide,palmit-amide, amides of hydrogenated tallow fatty acids, variouscommercially produced mixtures of palmitamide and stearamide arespecially useful in carrying out my invention. Included in thisdefinition are amides of these fatty acids which have a .carboxamidegrouping substituted on the beta carbon atom of the fatty amide chain.'I hus, dodecyl succinamide is a useful amide for the purposes of thisinvention.

As formaldehyde, I may use various aqueous solutions of formaldehydesuch as formalin or more highly concentrated solutions which may alsocontain methanol. Various polymers of formaldehyde, such as polyoxymethylene or paraformaldehyde are particularly useful. Formaldehydecontaining substances which yield their formaldehyde readily may also beused, such as methylal or methylol urea.

'Ihe urea used in my compositions may be introduced as crystal urea or Imay use its mxiture with formalin.

A number of amines are suitable for the preparation of my compositions.It has been found that primary mono, and diamines with a carbon chainlength (for each amino group) not over 4 carbon atoms are suitable. Whenlonger chain amines are tried in my compositions I have experienceddifiiculty in obtaining suitably stable dispersions for application tofabric. On the other hand, hydroxyalkyl amines containing up to 4 carbonatoms are especially useful in formulating compositions impartingdurable crease resistance and low chlorine damage to fabric. Ether andpolyether derivatives of these hydroxyalkyl amines containing one or twoamino groups have also been found to be especially useful.

As examples of the amines falling within these classifications thereare, monomethyl amine, monoethyl amine, monopropyl amine, monoisopropylamine, monobutyl amine, 1,2-ethylene diamine, 1,2- and1,3-diaminopropane, 1,4 diaminobutane, 1,5 diaminopentane, 1,6 diaminohexane, ethanolamine, 3-aminopropau0l-1, V l-aminopropanol-Z,3-(hydroxyethoxy)-propyl amine, and ether amines of the formula HOCH CHO(CH CH O) CH CH CH NH where x is an integer from 1-10, and thesO-called polyglycol diamines of the formula NH CH O CH CH O (CH NHwhere y is an integer from 1-5.

The ingredients of my compositions may be combined in a number of waysand under various conditions. It is convenient to put all materialstogether in a suitable reaction vessel where the mixture is stirred andheated to bring about interaction. If desired the amine, urea andformaldehyde may be reacted followed by addition of the amide and itsincorporation with the compositions. When the mixture" contains waterthe reaction may be run at temperatures suificient to bring aboutrefluxing of the Water. When only a small amount of water has beenintroduced the mixture may be reacted at temperatures of 75 to 150 C.

After a reaction time of 15 minutes to 4 hours depending on conditionsand ingredients, the products are convenientl'y mixed with water to formsolutions or dispersions of a pasty, viscous consistency. These aqueouscompositions are then diluted further in making up a bath forimpregnation of the fibrous material.

It has been found important to use certain restricted ratios ofingredients in order to obtain compositions with optimum properties. Theratio of formaldehyde to urea should be between 3:1 and 5:1 on a molarbasis. Similarly 0.25 to 1.0 mole of amine per mole of urea should bereacted and the molar ratio of fatty amide to amine should be betweenabout 0.50 and 2.0.

Certain conjectures have been made concerning the mode of reaction andthe structures present in the compositions which are disclosed by thisdescription. The amine, formaldehyde and urea probably interact to formcondensation products whose structure may be represented by thefollowing formula:

Urea formaldehyde condensation products are also involved. They probablyconsist of methylol urea and dimethylol urea or their condensationproducts with themselves or the amine containing product.

It is known that the fatty acid amide is also combined formaldehyde andit is believed that the resulting methylol compound has probablycondensed with the other condensation products formed from the otheringredients.

Accordingly, it appears impossible to state exactly the structuralconfiguration of the compositions. If the ratios of ingredients are heldto those mentioned above it would appear that the proposed structureswill be present in the final product in quantities which depend on theratios of reactants.

It is important that the compositions prepared by the interaction of theingredients described above be dispersed in water so that they may bereadily applied to fibrous materials. Usually this is readilyaccomplished by mechanical agitation with water at temperatures of about50-90" C. Adjuvants possessing surface activity may be used in order toaid dispersion. Up to five percent of such materials may be usedfor-this purpose. For example, I may use aryl sulfonic acids, ethyleneoxide condensates, fatty esters of polyols and the like. Sometimes I mayincorporate a small amount of a fatty acid into my formulation tofacilitate the preparation of dispersions of the final products. Suchacids as stearic or oleic may be used for this purpose.

In the following examples I have described the preparation of my novelcompositions, the parts being given by weight.

All of these ingredients except 53 parts of water are charged to areaction vessel having a mechanical stirrer and a reflux condenser. Themixture is heated at 220 F causing slight refluxing, and stirred for 2hours. The water which has been held out from the mixture is now addedslowly with agitation. The resulting paste is smooth and white and aftercooling to room temperature is usable in the processing of textilematerials as described in later examples.

EXAMPLE 2 Parts Stearamide 234 Para-formaldehyde (containing 91% CH O)154.6 Urea 70.3 Monisopropanolamine 86.6 Stearic acid e 7.0 Water 55.0

The ingredients are treated as in Example 1. The product is a whitepaste, dispersible in water.

EXAMPLE 3 Parts Hydrogenated tallow amide a 234.0 Paraformaldehyde(containing 91% CH O) 154.0 Urea 70.3 Monoethanolamine 35.3 Stearic acid7.0 Water 55.0

The materials of this example are reacted together as in Example 1. Theproduct is a creamy white paste which is dispersible in water.

EXAMPLE 4 Parts Stearamide 140.7 Parafonmaldehyde (containing 91% CH O)93.0 Urea 42.22 Monoethylarnine 21.90 Water 21.1 Polyoxyethylenes-tearate 18.00 Water 267.16

The first five materials are heated under reflux conditions for onehour. Then the polyoxyethylene stearate and water are added withagitation. The product is an easily dispersible paste.

EXAMPLE 5 Parts Hydrogenated tallow amide 200 Paraformaldehyde(containing 91% 'CH;;()) 132 Urea 3-(2-hydroxyethoxy) -propyl amine 60Water 47 The ingredients are reacted as in Example 1 except that 40parts of water are withheld until the reaction has been completed. Afteraddition of this portion of water and cooling the product is a white,dispersible paste.

The following examples illustrate the application of the products ofthis invention to textile fabrics and describe the eifects producedthereon.

In general, these products are applied from dilute aqueous dispersionsusing a padding technique in which the textile material is passedthrough the aqueous bath, passed through squeeze rolls (this sequencemay be done twice if necessary) and then heated to remove water andthereafter cured by further heating. After this curing 5, operation thefabric may be afterwashed or treated in any required manner.

The proper application of the products of this invention requires theuse of a catalyst in the padding bath. The catalyst remains on thefabric to catalyze (or accelerate) the reactions which take place on thefabric. Sufiicient curing is necessary to obtain durable waterrepellency and this depends on the nature of the fabric, the weight ofthe fabric, the type and quantity of catalyst, the time and temperatureof curing. Catalysts useful in applying these products are acidic orpotentially acidic materials such as zinc nitrate, organic acids (e.g.tartaric acid), hydrochlorides of amines, metallic halides (e.g.magnesium chloride), acid salts such as phosphates and the like.Sometimes certain neutral salts are operative, such as for examplemagnesium sulfate.

The amount of product left on the fabric depends on the concentration inthe bath and the amount of this bath picked up by the fabric (wetpickup). Suitable concentrations of my compositions in the pad bath maybe from 1% to 50%. Usually high concentrations are not necessary toobtain very satisfactory spray ratings so that concentrations of 3% to15% are normally applied. Low concentrations, say 0.5 to 3% are usefulif softening without water repellency is desired.

Catalyst concentration may vary considerably depending on the catalystchosen. When zinc salts are used they are used at about 5 to 25% of theconcentration of the product used.

In showing the effectiveness of these applications certain tests havebeen made:

Water repellency is tested by AATCC Standard Test Method 22-1952. Theresults are given by spray rating; a. spray rating of 100 indicates thatunder the conditions of the test the fabric is completely repellent tothe test spray.

Crease resistance is measured by applying AATCC Tentative Test Method66-1956. The results reported in the examples below are given as theMonsanto crease angle where the warp and fill figures are addedtogether. Tensile strengths are obtained by a grab tensile testdescribed by ASTM Standard Method D-39-40. Tensile strengths in the warpdirection are reported.

EXAMPLE 6 The preparation of Example 1 was dispersed in water. The bathcontained the indicated amount of zinc nitrate. Cotton sheeting (80 X80) was impregnated by passage through a laboratory padder with rollsadjusted to yield 100% wet pickup. The fabric was then dried at 180 F.and cured at 325 F. for 90 seconds. The results of laboratory tests wereas follows:

Spray rating Percent Percent Crease product of zinc angle Examplenitrate Original 1 laun- 5 laun- (original) 1 dering 1 derings I 1 AATCCStandard Test Method 36-1957 No. 3 at 160 F.

A viscose rayon challis having a warp tensile strength of 68 lbs. wastreated with this 'bath, applying 115% wet pickup. The impregnatedfabric was dried at 180 F.

6 and cured at 315 F. for five minutes. fabric indicated the following:

Testing of the Tensile Spray rating strength Fabric (lbs) after 5 laun-After dcrings. Original 5 launderings 1 Treated 70 100 -100 Untreated 500 0 1 Laundered in home washer at 140 F.

EXAMPLE 8 A light weight chlorinated wool challis fabric was paddedthrough a bath (formulated below) at wet pickup, dried at 180 F. andcured at 300 F. for three Mixtures of fibers are amenable to treatmentas described in this example. A polyester-viscose fabric containing 65%of the former and 35% of the latter was impregnated in a bath containing8% of the product of Example 1, 0.1% of 56% acetic acid and 1.5% of azinc nitrate containing catalyst known commercially as Catalyst H-7. Thewet pickup was 80%. The fabric was dried at 180 F. and cured at 305 F.for 90 seconds. The fabric so treated retained a spray rating of 100,even though exposed to 5 automatic launderings at F.

EXAMPLE 10 A cotton-viscose upholstery fabric (35% cotton-65% viscose)was padded through a solution consisting of 10% of the product ofExample 3, 0.1% of 56% acetic acid and 1% zinc nitrate (90% wet pickup)dried and cured at 315 F. for 3 minutes.

A spray rating of 80-90 was obtained on treated fabric compared with anuntreated fabric showing zero spray rating. In addition, a considerabledegree of dimensional control was obtained.

EXAMPLE 11 A cotton drapery fabric was treated in a bath containing 10%of the product of Example 1 and 1% of zinc nitrate catalyst. The wetpickup was 100%. The fabric was dried at 180 F. and cured for 90 secondsat 310 F. The fabric was then tested for water repellency, showing aspray rating of 100. It was then dry-cleaned and washed with Water anddried. The spray rating was then 90100. After three more dry cleaningsfollowed by water washing it had a spray rating of 80.

It is a known fact that commercial dry cleaning tends to leave residualamounts of wetting agents in the cleaned fabric. This obviously lowersthe spray rating. If these residual wetting agents are washed out withwater or dry cleaning solvent the true water repellent effect of thefinish on the fabric is observed. In this way the real durability of thefinish is made apparent.

In another experiment 80 x 80 cotton sheeting was treated at 100% Wetpickup with a bath containing 8% of the product of Example 1 and 0.8% ofzinc nitrate.

The dried fabric was cured at 310 F. for 90 seconds. The spray ratingafter curing was 100. After one dry 8 Preparation B was used with thenovel compositions of this invention as follows:

cleaning followed by washing with clean trichloroethylene Parts thespray rating was 70. After 3 commercial dryclean- Preparation B 8 ingsfollowed by three 33-minute washes in clean trichloro- Product ofExample 1 5 ethylene the spray rating was 50. Zinc nitrate 0.8 In theexamples just cited treatment of textile fabrlc Acetic acid 0.05 hasbeen by my novel compositions alone. In the e Wa r 35-15 amplesw.hlc.h.fouow conjoint use wlth Vanous other The above mixture was usedto impregnate 80 x 80 cotfabnc fimshmg agents 15 Illustrated 10 tonsheeting at 100% wet pickup. The fabric was cured EXAMPLE 12 for 90seconds at 300 F. after drying at 180 F. The A triazone type finishingcomposition such as that defabric gave the following test results: 7scribed in my copending application Serial No. 665,138 now U.S. Patent2,917,411 may be used in conjunction 15 Spmymtmg g gzg Tensile with thenovel products of this invention. Such a com- Fabric Orig. strength,position is described as Preparation A. 1 1 d 1 5 d 1 d Orig 1 dPreparation A 311K]. 3.1111 31111 31111 Parts Teat d 90400 100 so so 28726G 41 garaformaldehyde (Containing 91% 2 2( uhne atiifl: 0 o 0 0 180172 66 rea Water 128 Monoethanolamine 30.5 These figures indicate that adurably water repellent,

' crease-resistant fabric was obtained. The wash-Wear ap- Z iif; 2 2$;iixf giz g gggi i gz g zg g g pearance of this treated fabric wasexcellent and durable. hours. A clear solution resulted which was cooledand EXAMPLE 14 neutralized to pH 7 with 75% phosphoric acid. This I nthis example 80 x 80 cotton sheeting was impregwas g f fi of Example 1 mthe following nated with the product of Example 4 alone and with amouSan P t 30 Preparation A. The fabric was padded at 100% wet P d t f E 11 8 pickup, dried at 180 F. and cured at 320 F. for 90 uc Z e 5 seconds.The spray rating, crease resistance and warp fig g g 0 75 tensilestrengths were found to be as indicated in the table. Water 8425Composition of Bath This mixture was used to impregnate 80 x 80 cottonsheeting at 100% wet pickup. The sheeting was cured I, percent II,percent at 325 F. for 90 seconds after drying at 180 F. The test resultswere as follows: Product of Example 4 10 5 Preparation A 5 peticrttTcid8. g5 35 me Ill 3. e

Spray rating Chlorine damage, Properties 0] Fabric Crease percent Fabricresist- Orig. llaund. filaund. ance After 5laund5' I H Control washsCrease rctsistance (after 1 laundering) 284 259 174 pray ra mgor1g1na 0100 0 Treated 100 95 80-85 276 6 10 t o o 0 163 1 3 Iiiifiiii figifiglljlllliilll 33 i3 42.4 43.2 65

ittiSS h 25%; 3

EXAMPLE 15 It should be noted that the low chlorine damage, even TheProduct, was dispersed in a bath after multiple laundering, is of valuein application of mg followmg composition: these products to whitefabrics which ordinarily are P t bleached in normal washing. Product ofExample 5 4 EXAMPLE 13 i g 8-? cc 1c am 0 A melamine modifiedpolyformal, such as those de- Water' 954 scribed in my copendingapplication Serial No. 625,241 u now U.S. Patent 2,895,923 was prepared(Preparation Cotton shfietmg was lmpregnated Wild} thls bath B) and used'with the compositions of my invention in treated as m Eample The Spraymung on the fabnc this example 7 before laundering was 95-100, afterfive launderings the Preparation B ratlng WiS 80. Cotton sheeting nottreated shows a zero Parts spray ra mg. parafol-maldehyde (containing91% CHZO) 79 The foregoing descript ons and examples show plainlymethylene glycol 13 3 how the products of my invention may be applied tocel- Melamine 24 1 10 e fabncs such as those made from cotton orregenerated cellulose and combinations thereof. Their applica- Theparaformaldehyde and the diethylene glycol were tion to wool has alsobeen illustrated. They have been mixed and heated together to form aclear solution. found useful when applied to fibers of silk, celluloseace- The melamine was added and the mixture stirred and tate, andhydrophobic fibers such as nylon, polyester, heated until a clearsolution resulted. saran, acrylic and olefin.

I claim:

1. A textile finishing composition comprising an aqueous dispersion ofthe products of interaction at reflux temperatures of (a) an amide of -along chain fatty acid having 8 to 35 carbon atoms, (b) formaldehyde,urea and (d) a saturated primary amine containing not more than twoamino groups in which the NH groups are attached to a radical selectedfrom the group consisting of monovalent and divalent hydrocarbonradicals having not more than four carbon atoms for each amino groupattached thereto, monovalent and divalent radicals having not more thanfour carbon atoms and having one hydroxyl substituent, radicals havingnot more than four carbon atoms and having a polyether substituent ofthe formula HO(CH CH O) -where x is an integer from 1 to 10, andradicals of the formula Where y is an integer from 1 to 5; the molarratio of reacting substances being taken so that the ratio of formal- 10dehyde to urea is between 3:1 and 5:1; the ratio of amine to urea isbetween 0.25:1 and 1.0:1 and the ratio of amide to amine is between0.521 and 2.0: l.

2. A textile finishing composition as defined in claim 1, wherein theamide is stearamide and the primary amine is a monoalkylolamine.

3. A textile finishing composition as defined in claim 1 containing asmall amount of a higher fatty acid as a dispersant.

References Cited in the file of this patent UNITED STATES PATENTS2,547,728 Abrams Apr. 3, 1951 2,617,744 Dixon NOV. 11, 1952 2,693,460Gagliardi Nov. 2, 1954 2,917,411 Kress Dec. 15, 1959 2,923,698 Rust Feb.2, 1960 2,944,921 Groves et a1 July 12, 1960

1. A TEXTILE FINISHING COMPOSITION COMPRISING AN AQUEOUS DISPERSION OFTHE PRODUCTS OF INTERACTION AT REFLUX TEMPERATURE OF (A) AN AMIDE OF ALONG CHAIN FATTY ACID HAVING 8 TO 35 CARBON ATOMS, (B) FORMALDEHYDE, (C)UREA AND (D) A SATURATED PRIMARY AMINE CONTAINING NOT MORE THAN TWOAMINO GROUPS IN WHICH THE NH2 GROUPS ARE ATTACHED TO A RADICAL SELECTEDFROM THE GROUP CONSISTING OF MONOVALENT AND DIVALENT HYDROCARBONRADICALS HAVING NOT MORE THAN FOUR CARBON ATOMS FOR EACH AMINO GROUPATTACHED THERETO, MONOVALENT AND DIVALENT RADICALS HAVING NOT MORE THANFOUR CARBON ATOMS AND HAVING ONE HYDROXYL SUBSTANTIALLY, RADICALS HAVINGNOT MORE THAN FOUR CARBON ATOMS AND HAVING A POLYETHER SUBSTITUTENT OFTHE FORMULA HO(CH2CH2O)X-WHERE X IS AN INTEGER FROM 1 TO 10, ANDRADICALS OF THE FORMULA